Anthraquinone compounds



Patented Aug. 29, 1944 AN THRAQUINONE COMPOUNDS Joseph B. Dickey,Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., acorporation of- New Jersey No Drawing.

Claims.

This invention relates to new anthraquinonecompounds useful for thecoloration of organic derivatives of cellulose, particularly organicderivative of cellulose textile materials. Coloration can be eifeoted bydyeing, printing, stencilthe coloration of cellulose acetate, a materialto which the invention is especially adapted, it will be understood thatit applies to the coloration of other Organic derivatives of cellulosesuch as those just mentioned.

The anthraquinone compounds of my invention have the general formula:

H i a r wherein R represents a member selectedfrom the group, wherein X,X1 and X2 each represents, the residue of a member selected from thegroup consisting of an ethyl and a propyl group and R1 While myinventionwill be illustrated mor particularly in connection with ApplicationOctober 19, 1940, Serial No. 361,975

' quinone.

represents an unsubstituted .alkyl radical, Y, Z

Washing. They are especially adapted for the dyeing of cellulose acetatesilk. By sulfonation of the compounds of my invention, in accordancewith known methods for the introduction of a sulfonic acid group into ananthraquinone nu-I cleus, sulfonated dye compounds are obtained whichare suitable for the coloration of silk and wool. e v

The preparation of the anthraquinone compounds of my invention variesdepending upon the particular compound desired. In general theanthraquinone compounds of my invention can be prepared by reacting anamine selected from the group consisting of amines having the generalformulae:

H2NX--O'X1OH,

H2NXOX1OX2-OH and H2N-XOX1OR1 wherein R1, X, X1 and X2 have the meaningassigned to them or an amine having one of the formulae just giventogether with a primary (alkyl-, hydroXyalkyl-, alkoxyalkyle, al1yl-,cyclo- .alkyl-, aralkyl-, phenylor furfurylamine with a leucou-substituted anthraquinone.

Leuco a-substituted anthraquinones that can be employed include theleuco forms of quinizarin, 1,4,5-trihydroxy anthraquinone, 1,4,5,8-tetrahydroxy anthraquinone, 1,4-di-, 1,4,5- tri-and 1,4,5,8tetraaminoanthraquinone, 1 amino-4-hydroxyanthraquinone, 1,4-dihydroxy-5,8 diaminoanthraquinone, 1 -hydroxy-4-alkylagmino-anthraquinone,l-hydroxy-l-furfurylaminoanthraquinone, 1,4-dialkylaminoanthraquinoneand 1-hydroxy-4-phenylaminoanthraquinone.

Anthraquinone compounds of my invention can also be prepared fromcertain unreduced anthraquinone' derivatives such as 1 -amino-4-methoXy-anthraquinone, quinizarin, diaminoanthrarufin and1,5-dimethoxy-4,8'-diaminoanthra- In addition, certain anthraquinonescontaining replaceable nitro groups or halogen atoms when treated withthe desired amine or amines can be employed. Illustrative of theselatter compounds may be mentionedl-B-hydroxyethylamino-4-bromoanthraquinone and 1methylaminol-nitroanthraquinone.

Compounds of my invention containing a B- hydroxy-B-ethoxyethylamino or'a fl-hydroxy-W- ethoxy-,B-ethoXyethylamino group, for example, in the1-position and a hydroxy group in the 4- position can be prepared bycondensation of -1 mol equivalent of leuco quinizarin with 1 moleequivalent of B-hydroxyethoxyethylamine orchydroxy-fi'-ethoxy-[i-ethoxyethylamine. Where both the 1- and4-positions of the anthraquinone nucleus are to be substituted Witheither one of the groups named, one mole equivalent of leuco quinizarinis condensed with 2 mole equivalents of the amines. Where both of theamine groups named ar to be present, condensation may be efiected withboth amines present or two separate condensations may be carried outeach of the tWo separate condensations being carried out with but oneamine present whereby condensation is effected with first one and thenthe other amine. Where one of th amine groups named is to be present inthe 1-position and one of the other amino groups named hereinbefor'e isto be present in the 4-position, the groups may be introduced in onecondensation, or two separate condensations may be carried out similarlyas indicated above.

The condensation reactions referred to above may be carried out in waterbut ordinarily they are conducted in the presence of a solvent diluentsuch as ethanol, butanol or pyridine. The leuco dye compounds formed bythe condensation reactions may be oxidized with air or other suitableoxidizing agents such as sodium perborate or sodium chlorate, forexample, in known fashion to obtain the desired dye compounds.

Alkoxyalkylamines and hydroxyalkoxyalkylamines that can be employed inth preparation of the anthraquinone dyecompounds of my invention include,B-hydroxy-p-ethoxyethylamine,

H2NCH2CH2OCH2CH2OH p-hydroxy-B'-ethoxy-p-ethoxyethylamine,

I-lzNCI-IzCH2OCH2CI-I2OCH2CHzOI-I B methoxy p-ethoxyethylamine,

H2N-+CH2CH2-O-CH2CH2OCH3 B-ethoxy-Bethoxyethylamine,

H2NCH2CH2OCH2CH2OC2H5 p-butoxy-p-ethoxyethylamine,

H2NCH2CH2OCH2CH2-OC4H9 'y-hydroxy-v-propoxy propylamine,

H2N--CH2CH2CH2OCH2CH2CH2OH 'y-hydroxy-v-propoxy-=v-propoxy propylamine,

p hydroxy-p-propoxy propylamine,

rnN-om'onona,

' o-omcnonore I p-hydroxy-p-propoxy ethylamine,

H2NCH2CH2-O-CH2CHOHCH3 [#hydroxy-p'-propoxy-,6-propoxy propylamine,

HgN-CHzGHCHa -QHaCHCHs -CHCHOHCH3 -y-methoxy-- -propoxy propylamine,

. H2NCHzCHzCH2OCH2CHzCH2-OCH3 and ,c-ethoxy-p-propoxy propylamine,

mN-omonona OHCHOH3 During the investigation of the compounds of myinvention, I have discovered that if certain having very advantageousproperties are ob- Example 1 24 grams of leuco quinizarin are heated in200 cc. of butanol with 10.5 grams of fi-hydroxy-p- 'ethoxyethylamine'for 4 hours. The resulting leuco dye is poured into water and oxidizedwith sodium perborate. The dye compound obtained, l-fi-hydroxy-B-ethoxyethylamino 4 hydroxyanthraquinone is recovered by filtration, Washedwith water and dried. It colors cellulose acetate silk violet. 1

By the substitution of 27.2 grams of leuco1,4,5',8-tetrahydroxyanthraquinone for the leuco quinizarin of theexample, l-p-hydroxy-fi-ethoxyethylamino-4,5,8-trihydroxyanthraquinoneis obtained. This dye compound colors cellulose acetat silk purple.Similarly, if equivalent gram molecular weights ofc-hydroxy-p'-ethoxy-;3- ethoxyethylamine,'y-hydroxy-y-propoxypropylamine and ,6-hydroxy-p-propoxypropylamine areused in place of B-hydroxy-e-ethoxyethylamine 35 and rea'ctedwith leucoq'uinizarin, l-p-hydroxy- [3'-ethoxy-p-ethoxyethylamino-4-hydroxyanthraquinone, l-'-hydroxy-'y-propoxypropylamino-4- hydroxyanthraquinone andl-fl-hydroxy-e-propoxypropylamino-4-hydroxyanthraquinone a r e obtained.

- Example 2 24 grams of leuco quinizarin are refluxed in 200 cc. ofbutanol together with 22 grams of c-hydroxy-p-ethoxyethylamine for 4hours. Upon 'working up in accordance with the method described inExample 1, 1,4-di-mono-fl-hydroxy-5- ethoxyethylaminoanthraquinone isobtained. This dye compound colors cellulose acetate silk blue.

Example 3 '24 grams of leuco quinizarin, 10.5 grams ofphydroxy-p-ethoxyethylamine, grams of18-hydroxy-p-ethoxy-5-ethoxyethylamine and 200 cc.

' of butanol are refluxed together for 4 hours and Example 4 '6 grams ofleuco quinizarin, 18 grams of quinizarin, 3.2 grams of methylamine, 200cc. of bumixtures of amines are employed, dye mixtures tanol and 10.5grams of fi-hydroxy-p-ethoxyethylamine arerefiuxed together for 4 hoursand the reaction mixture is 'workedup in accordance with the proceduredescribed in Example 1. l-p-hydroxy- ,6 -ethoxyethylamino 4methylaminoanthraquinone is obtained and colors cellulose ace tate silkblue.

By the substitution of an equivalent gram molecular weight ofethylamine, n-propylamine, isopropylamine, butylamine, cetylamine andphydroxy-p-propoxy-[i-propoxypropylamine f or the methylamine of theexample, anthraquinone compounds, in which the methylamine group isreplaced by an ethylamino, n-propylamino, an isopropylamino, abutylamino, a cetylamino and a fl-hydroxy- ,8 propoxy ppropoxypropylamino group, respectively, are obtained.

Example 5 G-grams of leuco quinizarin, 18 grams of quinie zarin, 200cc.of pyridine, grams of cyclohexyl-' 24 grams of leuco 1,4-diaminoanthraquinone, 200 cc. of butanol, 10.5 grams of.p-hydroxy-dethoxyethylamine and 6 grams of allylamine are refluxedtogether for 4 hours and the reaction mixture is worked up as describedin Example 1. 1 e-hydroxyB-ethoxyethylamino 4 allylamino anthraquinoneis obtained and colors cellulose acetate silk blue.

Example 7 24 grains of leuco 1-hydroxy-4-aminoanthra quinone, 400 cc. ofethanol, grams of ,B-hydroxy (3' ethoxy B ethoxyethylamine and 11 gramsof benzylamine are refluxed together for 6 hours and the reactionproduct is worked up in accordance with the procedure described inExample 1. vl-pr-hydroxy-q?-ethoxyli-ethoxy-,ethylamino-4-benzylaminoanthraquinone is obtained and colors celluloseacetate silk blue. I

Example 8 24 grams of leuco quinizarin, 250 ccJof butanol and 11 gramsof p-phenylenediamine are heated under reflux for 10 hours. Followingthis, 11 grams of ,B-hydroxy-fi-ethoxyethylamine are added and refluxingis continued until no further color change takes place. The reactionmixture is Worked up in accordance with the procedure described inExample 1. l-p-hydroxy-fi-ethoxyethylamino 4 -(4'-amino)phenylaminoanthraquinone is obtained and colors cellulose acetate silkbluish-green. If desired, boric acid or a mixture of boric acid andsodium chlorate may be employed in the reaction as catalysts.

Example 9 grecovered by filtration.

Example 1 0 25.3 grams of 1-amino-4-methoxyanthraquinone are dissolvedin butanol heated to 110 C. and 10.5 grams ofp-hydroxy-p-ethoxyethylamine are added dropwise over a period of 2 hoursfollowed by heating for an additional hour. The dye compound isprecipitated by. concentrating the reaction mixture following which itcan be l-e-hydroxy-fl-ethoxyethylamino-4-aminoanthraquinone is obtained.It colors cellulose acetate silk reddish-blue.

Example 11 31.3 grams of 1-,B-hydroxyethylamino-4-bromoanthraquinone areheated in pyridine in an autoclave at 200 C. with 40 grams offl-hydroxye-ethoxyethylamine for 20 hours. l-p-hydroxyaminoanthraquinoneis recovered from the reaction mixture and colors cellulose acetate silkblue.

Example 12 I Z'Z' gramsof 1,5 diamino 4,8-dihydroxyanthraquinone areheated with 250 grams of p-hydroxyi-ethoxyethylamine at 100-160 C. untilno fure ther color change towards blue-green takes place. Water is thenadded to the reaction mixture and the precipitated dye compound isrecovered by filtration, washed with water and dried.1,5-dimono-;3-hydroxy-fl-ethoxyethylamine-4,8- diaminoanthraquinone isobtained and colors cellulose acetate silk greenish-blue.

Example 13 2'7 grams of leuco 1,4,5,8-tetraaminoanthraquinone are heatedin 250 cc. of butanol together with 25 grams of{3-hydroxy-fi-ethoxyethylamine under reflux for 10 hours. The resultingleuco dye compound is worked up as described in Example 1.1,4-di-mono-5-hydroxy-fl-ethoxyethylamino-5,8-diaminoanthraquinone isobtained and V colors cellulose acetate silk greenish-blue.

. butanol.

Example 14 To a mixture of 1.94 grams of leuco quinizarin, 3.35 grams of86% quinizarin and 0.35 gram of sodium carbonate Was added a mixture of1.32 grams of fi-hydroxy-pl-ethoxyethylamine and 2.73 grams of 33.3%methylamine in 20 cc. of n- The reactants were refluxed for 10 hours andthen oxidized by adding 5 cc. of water and 2.5 grams of sodium perborateto the hot reaction mixture and heating for one hour. The dye productwas recovered by pouring the reaction mixture into one and one-halfliters of hot water, stirring, filtering, washing with water and drying.The dye mixture obtained consists essentially of anthraquinone compoundssubstituted only in their 1 and 4 positions with a monomethylamino groupor a mono fi-hydroxy-pethoxyethylamino group,'said groups being presentin the ratio of 3 mole parts of the mono-phydroxy-p-ethoxyethylaminogroup to 7 mole parts of the'monomethylamino group. The product obtainedcolors cellulose acetate silk blue.

Example 15 8-10 hours and then'oxidized by adding 5.cc. of water and 2.5grams of sodium perborate portionwise to the hot reaction mixture andheating for one hour. The reaction mixture was then poured into one andone-half liters of hot water, stirred, filtered and the dyemixturerecovered by filtration, washed with Water and dried. The dyemixture obtained consists essentially of anthra-' To a mixture of 2.2grams of leuco 1,4,5,8-

tetra-hydroxyanthraquinone and 0.35 gram of,

sodium carbonate was added a mixture of 1.32

grams of [3-hydroxy-,Bethoxyethylamine and 2.73 grams of 33.3%methylamine in 20 cc. of butanol. The reactants were refluxed for tenhours and then oxidized by adding 5 cc. of water and 2.5 grams of sodiumperborate por'tionwise to the hot reaction mixture and heating for onehour. The reaction mixture was poured into water and the dye mixtureformed by the reaction, recovered by filtration, washed with water anddried. Thedye mixture obtained consists essentially of anthraquinonecompounds substituted in both their 5 and 8 positions with a hydroxygroup and substituted in their 1 and 4 positions with a monomethylaminogroup or a mono-,e-hydroxy-fl-ethoxyethylamino group said groups beingpresent in the ratio of 7 mole parts of the monomethylamino group to 3mole parts of the mono -phydroxy 43- ethoxyethylamino group, and colorscellulose acetate silk greenishblue.

Erample 17 To a mixture of 1.94 grams of leuco quinizarin, 3.35 grams of86% quinizarin and 0.35 gram of sodium bicarbonate was added a mixtureof 1.68 grams of e-ethoxy-fl-ethoxyethylamine and 2.73 grams of 33.3%methylamine in 20 cc. of nbutanol. The reactants were refluxed for hoursand then oxidized by adding 5 cc. of water and 2.5 grams of sodiumperborate portionwise to the hot reaction mixture and heating for onehour. The reaction mixture was then poured into one and one-half litersof hot water, stirred and the precipitated dye product recovered byfiltration, washed with water and dried. The dye mixture obtainedconsists essentially of an-. thraquinone compounds substituted only intheir 1 and 4 positions with a monomethylamino group or amono-c-ethoxy-e-ethoxyethylamino group said groups being present in theratio of '7 mole parts of the monome thylamino group to 3 mole parts ofthe mono-pethoxy-,B-ethoxyethylamino group, and colors cellulose acetatesilk'blue. The dye mixture obtained begins to soften at 120 C. andsludges and melts at I'M-185 C. 5.3 grams or an 80.8% yield wasobtained.

.1 gram mole of -hydroxy- -propoxy-' -propoxypropylamine, ,B' hydroxy 43propoxyethylamine, fi-hydroxy-e'-propoxy-,8-propoxypropylamine,-methoxy- -propoxypropylamine or pethoxy-,B-p-ropoxypropylamine, forexample, can be reacted with .1 gram mole of leuco quinizarin in thepresence of a solvent such as butanol in accordance with the proceduredescribed hereinbefore to obtain l- -hydroxy- -propoxy -'propoxypropylamino-4 hydroxyanthraquinone, 1 5- hydroxy -ppropoxyethylamino 4 hydroxyan l-c-hydroxy-e'epropoxy {3 prothraquinone,poxypropylamino-4-hydroxyanthraquinone, 1-ymethoxy- -propoxypropylamino4 hydroxyanthraquinone andl-p-ethoxy-,3-propoxypropylamino-4-hydroxyanthraquinone, respectively.

Additional dye compounds which can be prepared in accordance with myinvention include.

methylamino-4,5-di-fl-hydroxy p ethoxyethylamino-8-hydroxyanthraquinone.These compounds color cellulose acetate silk bluish green. Additionaldyes which yield greenish-blue.

shades on cellulose acetate silk include 1,4-die-hydroxyv -eethoxy 8ethoxyethylamino-5,8- dihydroxyanthraquinone and 1-e-hydroxy-5- ethoxy,8 ethoxyethylamino-4-,6-hydroxyethyl amino-5-aminoanthraquinone.

The unsulfonated compounds of my invention,

as previously noted, can be sulfonated to yield dye compounds suitablefor the dyeing of wool and silk. Sulfonation can be effected usingchlorsulfonic or fuming sulphuric acid, for ex-' ample, to introduce oneor more sulfonic acid oups.

In order that the preparation of the compounds of my invention may beentirely clear, the preparation of various alkoxyalkylamines isindicated hereinafter.

Preparationof s-hydroxy-p-propoxy prom [amine One gram mole ofdi-propylene glycol, 20 grams of Raney nickel and 5 moles of ammonia arecharged into a shaking autoclave and heated with shaking at 220-240 C.for 20 hours. The autoclave is then cooled and the reaction mixtureremoved and distilled under reduced pressure. A good yield (35%) ofp-hydroxy-fi-propoxy propylamine and 0H3 CHZOH H2N(|JHCH20CHCHQ isobtained.

Preparation of e-hydrory- 3-ethoasyethyiamine ande-hydrory-p-ethoa:y-c-ethomyethylamine These compounds can be preparedby reacting one gram mole of diethylene glycoland triethylene glycol,respectively, with. ammonia in the presence of Raney nickel inaccordance with the procedure described above.

Preparation 0 -methoxy- -propozcy propylarm'ne and v-ethoxy- -propozcypropylamz'ne These compounds can be prepared by reacting one gram moleof HO(CHz)3O(CH2)sOCI-I3 and HO(CH2)3O(CH2)3OC2H5, respectively, withammonia in the presence of Raney nickel in accordance with the generalprocedure described hereinbefore. I

The glycols employed in the reaction can prepared by reacting twomolecular equivalents of trimethylene oxide with one molecular equiva- 1e -hydroxy-,8-ethoxyethylamino-4,5--dimethylamino-8-hydroxyanthraquinone and 1- I dye.

lent of methanol and ethanol, respectively, in an autoclave at atemperature of PIS-250 C.

Preparation of 'y-hydrozry-y-propoxy propylamine This compound can beprepared by reacting HO(CH2) 3O (CH2) 30H with ammonia. in the presenceof Raney nickel in accordance with the general procedure describedhereinbefore.

Preparation of p-methoxtl-fi-Prozicxy propylamine This compoundcan beprepared by reacting noomono'm OCH:

with ammonia in the presence of Raney nickel following the procedurewhich has been previously described.

The glycol employed in the above example can be prepared by heating twomolecular equivalent weights of propylene oxide with one molecularequivalent weight of methanol in an autoclave at a temperature of175-250 C.

Preparation of ,B-mcthozry-fi'-propoaiy-p-propoznfl propylamine Thiscompound can be prepared by reacting HOCHzCHCHa ocrnonom OCHzCHCHa OCHaocmcncm emotion, on

with ammonia in the presence of Raney nickel. The glycol employed inthis reaction can be purchased.

From the foregoing, the preparation of the alkoxy alkylamines employedin the manufacture of the anthraquinone dye compounds of my invention isbelieved to be clear to those skilled in the art. Other alkoxyalkylamines can be prepared in similar fashion;

The anthraquinone dye compounds of my invention can be applied to thecoloration of organic derivatives of cellulose such as cellulose acetatesilk by the well known dispersion method. In accordance with this methodof dyeing, the insoluble dye or dye mixture can be first ground to afine powder intimately mixed with a suitable dispersing or solubilizingagent following which the resulting mixture is added to wate or a dilutesolution of soap in water to form an aqueous dyebath. After this knownpreparation of the dyebath, the textile materials, for example, to bedyed may be added to the dyebath and the dyeing operation conducted inknown fashion. Suitable dispersing or solubilizing agents that can beemployed include soap, sulphoricinoleic acid, salts of sulphoricinoleicacid, a water solu alt thereof, such, for example, as the sodium orammonium salts.

The following example illustrates how dyeing may be carried out inaccordance with my invention. Quantities are expressed in parts byweight.

Example A 2 parts of the dye mixture of Example 14 are finely groundwith a dispersing agent such as soap or oleyl glyceryl sulfate and theresulting paste is dispersed in 1000 parts of water. The dispersion thusprepared is heated to a temperature approximating 45-55" C. and100 partsof cellulose acetate silk in the form of yarn or fabric, for example,are added to the dyebath after which the temperature is gradually raisedto -85 C. and the silk worked at this temperature until dyeing iscomplete. Sodium chloride may be added as desired during the dyeingoperation to promote exhaustion of the dyebath. Upon completion of thedyeing operation, the cellulose acetate silk is removed, washed withsoap, rinsed and dried. The cellulose acetate silk is colored a blueshade of excellent fastness to light, and washing.

While my invention has been illustrated in connection with the dyeing ofcellulose acetate silk, it Will be understood that dyeing operations canbe carried out in a manner similar to that described above by thesubstitution of another organic derivative of cellulose material forcellulose acetate silk or by employing dye compounds other than thoseemployed in the example or by substitution of both the material beingdyed and the dye compound of the example. Wool and silk can be coloredwith the anthraquinone dyes of my invention in accordance with themethods known tothe art for the coloration of these materials withanthraquinone dyes. It will be understood, however, that these materialscan be colored in accordance with the dispersion method of dyeing justdescribed.

I claim:

1. Anthraquinone compounds having the general formula:

wherein R2 represents an unsubstituted alkyl group;

3. Ananthraquinone dye mixture consisting essentially of anthraquinonecompounds substituted only in their 1 and 4 positions with a memberselected from the group consisting of a group and wherein said groupsare present in the ratio of 3 mole parts of the H N'-O2H4OOzH4OH groupto 7 mole parts of the H NCHs 4. An anthraquinone dye mixture consistingessentially of anthraquinone compounds substituted only in their 1 and 4positions with a member selected from the group consisting of a,

group and wherein said groups are present in the ratio of 3 mole partsof the H NCHa group.

5. An anthraquinone dye mixture consisting essentially of anthraquinonecompounds substituted only in their 1 and 4 positions with a memberselected from the group consisting of a H NCHa group.

JOSEPH B. DICKEY.

